CN114843007B - Method for preparing poly (3, 4-dioxyethylene thiophene) nano pattern by micelle etching - Google Patents
Method for preparing poly (3, 4-dioxyethylene thiophene) nano pattern by micelle etching Download PDFInfo
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- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
Abstract
The invention relates to a method for preparing poly (3, 4-dioxyethylene thiophene) nanometer patterns by micelle etching, which comprises the following steps of 1) treating a substrate, cleaning a glass substrate, removing impurities and hydroxylation, and placing the glass substrate in an environment with humidity of 40-80%; 2) Spin-coating an oxide film, dripping an oxidant solution onto a glass substrate, rotating the glass substrate, and standing for a period of time; 3) The method is simple to operate, convenient to control the size, high in stability, low in cost, and high in conductivity, and the size of holes on the nano patterns reaches the nano level.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a method for preparing a poly (3, 4-dioxyethylene thiophene) nano pattern by micelle etching.
Background
In the prior art, a regular cellular nano pattern is etched on a poly (3, 4-dioxyethylene thiophene) film by using hydroxy acid salt polystyrene nano spheres. In the prior art, an aqueous solution containing hydroxyl acid salt polystyrene nano-spheres is coated on a substrate (FTO, ITO, gold and the like) with conductivity, and after water is evaporated, a single-layer nano-sphere is spread and regularly arranged on the substrate. Then placing the substrate into a solution containing 3, 4-dioxyethylene thiophene (3, 4-dioxyethylene thiophene monomer), synthesizing by adopting an electrochemical method, growing poly (3, 4-dioxyethylene thiophene) in gaps in the nanometer microsphere array, then dissolving and washing the nanometer microsphere by using tetrahydrofuran solvent, and finally leaving a honeycomb poly (3, 4-dioxyethylene thiophene) pattern film.
The problems with this technique are mainly:
1. the technology has high implementation cost: the cost is high mainly due to the high price of the hydroxy acid salt polystyrene nano-spheres.
2. The technical implementation process is complex: the technical realization process comprises the processes of coating of nano-spheres, electrochemical synthesis, elution of the nano-spheres and the like, wherein the operation process has higher requirements.
3. Electrochemical synthesis requires that the substrate must be electrically conductive and not substantially compatible with this technology implementation.
The 3, 4-dioxyethylene thiophene monomer is subjected to liquid phase sedimentation polymerization on the surface of modified PI to prepare a poly (3, 4-dioxyethylene thiophene)/PI composite film and conductivity research, zhang Meijuan, university of south China and the university of south China, discloses a method for preparing the poly (3, 4-dioxyethylene thiophene) film, such as an electrochemical polymerization method, a physical coating method and an in-situ polymerization method, wherein the in-situ polymerization method comprises a direct polymerization method, a solution polymerization adsorption method, a chemical vapor deposition method, a vapor deposition polymerization method, a liquid phase sedimentation polymerization method and other polymerization methods, and the vapor deposition polymerization method is that a substrate with an oxidant film is placed in 3, 4-dioxyethylene thiophene monomer steam, so that 3, 4-dioxyethylene thiophene monomer molecules are subjected to oxidative polymerization to form a film on the surface of the substrate, and the fact that under an acidic condition, the 3, 4-dioxyethylene thiophene monomer has higher activity and weak alkaline pyridine and the like are required to be added to inhibit side reactions is disclosed. Adding a small amount of pyridine into n-butanol solution of iron p-toluenesulfonate, spin-coating the mixed solution and a glass substrate, drying at 80 ℃, transferring to 3, 4-dioxyethylene thiophene monomer steam saturated at 60 ℃ for reaction, and obtaining the poly (3, 4-dioxyethylene thiophene) film with the conductivity of 1354S/cm. Meanwhile, the defects of the method, namely the method is very sensitive to water vapor, the allowable fluctuation range of humidity is narrow, the product area is small, and the development requirement of a photoelectric device cannot be met.
Preparation of polyhydroxyl functionalized 3, 4-ethylenedioxythiophene film by chemical vapor deposition, performance study of the polyhydroxyl functionalized 3, 4-ethylenedioxythiophene film, zhang Xiaolan, etc., material development and application, and 2020.2 month published literature disclose specific methods, namely:
1. the substrate is sequentially put into detergent, deionized water, acetone, methylene dichloride and isopropanol for ultrasonic cleaning for 15min respectively, and then is put into a blast drying oven at 110 ℃ for drying. In order to increase the adhesiveness between the interdigital substrate and the oxidizer film, the substrate surface was treated with a plasma etching apparatus at a treatment power of 400W for 600s and a pressure of 25Pa.
2. And mixing the butanol solution and the oxidant solution, dripping the mixture into the center of the substrate, and spin-coating to obtain oxidant films with different thicknesses.
3. The oxidizer films of different thickness obtained by spin coating, 200mg of hydroxymethyl-3, 4-dioxyethylene thiophene were placed in a vapor deposition polymerization oven. And placing a proper amount of methanol (methanol vapor infiltrates the oxidant to keep the oxidant in an ionic state so as to oxidize the monomer) at one end of the quartz tube, vacuumizing, introducing nitrogen for 3 times, and removing oxygen in the quartz tube. Setting the deposition polymerization temperature at 80 ℃ for 4 hours, and carrying out deposition reaction under vacuum. And after the polymerization is completed, the temperature in the furnace is reduced to room temperature, the substrate with the poly (hydroxymethyl-3, 4-dioxyethylene thiophene) film is taken out, the substrate is put into methanol, the substrate is immersed for 10min and then is washed by a large amount of methanol, the residual unreacted oxidant and some oligomers are fully washed off, and the poly (hydroxymethyl-3, 4-dioxyethylene thiophene) film is obtained after the drying by nitrogen.
The film products are all a whole non-etched poly (3, 4-dioxyethylene thiophene) conductive film, so that no pattern is formed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing poly (3, 4-dioxyethylene thiophene) nano patterns by micelle etching, which has the advantages of simple operation, convenient size control, high stability, low cost, nano-scale hole size on the nano patterns and high conductivity.
The invention discloses a method for preparing poly (3, 4-dioxyethylene thiophene) nanometer patterns by micelle etching, which comprises the following steps,
1) Treating the substrate, namely treating the glass substrate by using mixed plasma gas of water and inert gas after the glass substrate is cleaned, removing and hydroxylating organic impurities on the surface of the glass substrate, and then placing the glass substrate in an environment with the humidity of 40-80% for a period of time to enable the glass substrate to absorb water until the water is balanced;
2) Spin-coating an oxide film, dripping an oxidant solution onto a glass substrate, controlling the temperature to be 8-12 ℃, rotating the glass substrate to form the oxidant film on the glass substrate, and standing for a period of time after rotation is completed; in the oxidant solution, the oxidant is ferric methylbenzenesulfonate, the solvent is n-butanol, and the oxidant solution also contains polyoxypropylene polyoxyethylene block copolymer (the molecular weight is preferably 2900 Da);
3) Forming poly (3, 4-dioxyethylene thiophene) nano patterns, placing a glass substrate with an oxidant film in a gas phase synthesis chamber, heating 3, 4-dioxyethylene thiophene monomers to form 3, 4-dioxyethylene thiophene monomer steam in the gas phase synthesis chamber, controlling the humidity in the gas phase synthesis chamber to be 35-45%, controlling the temperature to be 13-17 ℃, reacting for a period of time, cleaning, and drying to obtain the poly (3, 4-dioxyethylene thiophene) nano patterns.
In step 1), the glass substrate is cleaned by ultrasonic cleaning and then by using a mixed plasma gas of water and argon (the cleaning power is preferably 32 watts, the processing time is preferably 8 minutes, and the pressure is preferably 600 millitorr).
In the oxidant solution, the iron methylbenzenesulfonate has the mass concentration of 6 percent.
The mass concentration of the polyoxypropylene polyoxyethylene block copolymer in the oxidant solution was 0.1%.
The oxidizer solution also included 2wt% ethylene-bis-urethane glycol (diuthanediol).
In the step 2), the rotation control program of the rotating glass substrate is 500 rpm, 5 seconds; 2500 rpm, 30 seconds; 500 revolutions, 5 seconds.
In step 2), the standing time after the completion of the rotation is 2min.
In step 3), the heating temperature of the 3, 4-dioxyethylene thiophene monomer is 70 ℃.
In the step 3), the unreacted components are washed out by absolute ethyl alcohol.
In the step 3), the drying mode is that the sample is placed in a vacuum drying oven and dried in vacuum at the temperature of 80 ℃.
Compared with the prior art, the invention has the advantages of simple operation and low cost. In the invention, after the oxidant film is formed, the polyoxypropylene polyoxyethylene block copolymer in the oxidant film can automatically self-assemble with water molecules on a substrate to form nano micelle pellets, the nano micelle pellets can not chemically react with 3, 4-dioxyethylene thiophene monomer monomers, so that poly (3, 4-dioxyethylene thiophene) polymer can be generated only between the micelle pellets, the poly (3, 4-dioxyethylene thiophene) polymer can be washed out by ethanol, the micelle pellets can be removed, and nano holes are left on the poly (3, 4-dioxyethylene thiophene) film to form a poly (3, 4-dioxyethylene thiophene) netlike film with round holes, namely poly (3, 4-dioxyethylene thiophene) nano patterns.
After the surface of the glass plate is hydroxylated (hydrophilic), the glass plate is placed in a high-humidity environment, moisture is absorbed from air, the greater the air humidity is, the more moisture is absorbed by the surface of the glass, after a mixed oxidant film is prepared through spin coating, the condition of micelle formation is met by n-butyl alcohol/polyoxypropylene polyoxyethylene block copolymer/water=oil/amphiprotic/water, wherein the n-butyl alcohol and polyoxypropylene polyoxyethylene block copolymer exist in the film, the moisture exists on a glass substrate, and along with the coating of the film, the water on the glass substrate forms micelle pellets with the n-butyl alcohol and the polyoxypropylene polyoxyethylene block copolymer.
The poly (3, 4-dioxyethylene thiophene) nanometer conductive pattern is prepared by combining a gas phase synthesis method with a nanometer size micelle formed by an amphoteric macromolecule of a polyoxypropylene polyoxyethylene block copolymer. In the technology, the size of the pattern finally formed on the poly (3, 4-dioxyethylene thiophene) film can be controlled by only controlling the ambient humidity when the oxidant film is coated.
Compared with a non-patterned poly (3, 4-dioxyethylene thiophene) film, the poly (3, 4-dioxyethylene thiophene) nano pattern has larger specific surface area, and the poly (3, 4-dioxyethylene thiophene) nano pattern with the ultra-high specific surface area can be used for preparing high-sensitivity sensors and solar cells; in addition, the poly (3, 4-dioxyethylene thiophene) nanopattern of the present application can also be applied to the field of nanoseparation due to the nano-penetrating holes.
Compared with the prior art, the nano pattern penetrating through the whole film layer can be prepared by coating, synthesizing and cleaning, and the operation is simple and the difficulty is low.
The poly (3, 4-dioxyethylene thiophene) film is successfully patterned by a micelle etching method, and the hole size on the film reaches the nanometer level and can be obtained simply by controlling humidity; the electrical conductivity of the poly (3, 4-dioxyethylene thiophene) is high relative to other products of the same type; a patterned film of larger size can be prepared; low cost and high stability.
The product can be applied to electrochemical sensors, solar cells, optical devices and special separation membranes.
Drawings
FIG. 1 is a flow chart of the method of the present invention.
Fig. 2 is a schematic diagram of micelle formation.
FIG. 3 is a schematic diagram of the method of the present invention.
FIG. 4 is a topography of poly (3, 4-dioxyethylenethiophene) nanopatterns prior to cleaning.
FIG. 5 is a topography of the poly (3, 4-dioxyethylenethiophene) nanopattern after cleaning.
FIG. 6 is a scanning electron microscope image of poly (3, 4-dioxyethylenethiophene) nanopatterns (average film thickness of 61.4 nm).
FIG. 7 is a scanning electron microscope image of poly (3, 4-dioxyethylenethiophene) nanopatterns at 80% humidity.
FIG. 8 is a scanning electron microscope image of poly (3, 4-dioxyethylenethiophene) nanopatterns at 60% humidity.
FIG. 9 is a scanning electron microscope image of poly (3, 4-dioxyethylenethiophene) nanopatterns at 40% humidity.
FIG. 10 is a scanning electron microscope image of a poly (3, 4-dioxyethylenethiophene) nanofilm of comparative example 1.
Detailed Description
Example 1
A method for preparing poly (3, 4-dioxyethylene thiophene) nanometer patterns by micelle etching comprises the following steps,
1. cleaning a substrate: firstly, cleaning the glass plate by ultrasonic waves for 30 minutes to remove surface particles, then, adopting mixed plasmas of argon and water to remove organic matters on the surface of the glass plate, and grafting hydroxyl groups on the surface of the glass plate.
2. Treatment of hydroxylated glass substrates: placing the glass substrate in a rotary spin coater, regulating the ambient humidity (40% -80%), standing the glass substrate in the ambient humidity for 120 min (the effect of the step is that the hydroxylated glass substrate can fully absorb the moisture in the air until balanced under the corresponding humidity.)
3. Preparing an oxidant solution: firstly preparing n-butanol solution with the mass concentration of ferric methylbenzenesulfonate (the mass concentration is 6 wt%) and then sequentially adding 0.1wt% of polyoxypropylene polyoxyethylene block copolymer and 2wt% of ethylene-di-urethane glycol, stirring at room temperature for 60 minutes, then completely dissolving the ethylene-di-urethane glycol and the polyoxypropylene polyoxyethylene block copolymer, and finally forming an oxidant solution.
4. Formation of oxidant film: the oxidizer solution is dropped onto the glass substrate until the solution completely covers the glass substrate. Setting a rotating step, speed and time of rotating spin coating: 500 rpm, 5 seconds- >2500 rpm, 30 seconds- >500 rpm, 5 seconds, the ambient temperature during the coating process is controlled at 10+ -2deg.C. Through high-speed rotation, the excessive oxidant solution is thrown away, and finally a layer of oxidant solution film is formed on the glass substrate, and the coated oxidant film stands for 2 minutes (favorable for micelle formation).
5. Synthesis of poly (3, 4-dioxyethylenethiophene) nanopatterns: the poly (3, 4-dioxyethylene thiophene) nano pattern is synthesized by adopting a vapor phase synthesis method, and a glass substrate carrying a micelle oxidizing agent film is placed into a vapor phase synthesis reaction chamber. After the glass substrate is placed, a container containing 3, 4-dioxyethylene thiophene monomer is placed on a heating device at the bottom of a reaction chamber, after a door of a gas phase synthesis reaction chamber is closed, the temperature of the 3, 4-dioxyethylene thiophene monomer is heated to 70 ℃, the temperature in the synthesis reaction chamber is controlled to 15+/-2 ℃ (normal pressure), the humidity is controlled to 40+/-5%, the gas phase synthesis time is 30 minutes, after the reaction is completed, the unreacted complete oxidant component is washed out by absolute ethyl alcohol, and finally, a sample is placed in a vacuum drying box, and is dried in vacuum for two hours at the temperature of 80 ℃. The specific reaction process and principle are shown in figures 1-6.
Comparative example 1
Step 2) of example 1 was deleted, and the glass plate after ultrasonic cleaning in step 1) was directly put into a 110 ℃ drying oven for drying for standby. The other steps were the same as in example 1.
The glass plate of comparative example 1 was directly dried without any moisture on the glass plate, so that only a continuous film was formed instead of the pattern.
TABLE 1 influence of the glass plate treatment on the synthesis of the poly (3, 4-dioxyethylenethiophene) form
Experimental example 1
Controlling the step 2) in the example 1, adjusting the environmental humidity of the glass substrate to be 40%, 60% and 80% respectively when the glass substrate is kept still, and obtaining the scanning electron microscope images of the poly (3, 4-dioxyethylene thiophene) nano patterns as shown in figures 7-9. It can be seen that the maximum pore diameter (diameter) of the thin film is about 1.18 μm and the pore diameter distribution is uneven when the ambient humidity at the time of glass substrate treatment is 80%; when the environment humidity is 60% during the glass substrate treatment, the aperture of the film pattern is obviously reduced and more uniform; when the humidity is lower than 40%, the pattern disappears, forming a whole film.
The conductivity of poly (3, 4-dioxyethylenethiophene) nanopatterns under different humidity conditions was measured as shown in table 2.
TABLE 2 conductivity of poly (3, 4-dioxyethylenethiophene) nanopatterns under ambient humidity conditions for different glass substrate treatments
From the scanning electron microscope image and the conductivity analysis, the increase and decrease of the scanning electron microscope image and the conductivity analysis are inconsistent, and the larger the humidity is, the lower the conductivity is, and the larger the aperture is; the lower the humidity, the greater the conductivity, the smaller the pore size, the pore size distribution having the highest value at 60% humidity.
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the disclosure, including the claims, is limited to these examples; the technical features of the above embodiments or in the different embodiments may also be combined under the concepts of the present disclosure, the steps may be implemented in any order, and there are many other variations of the different aspects of one or more embodiments in this application as described above, which are not provided in detail for the sake of brevity.
The present application is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Any omissions, modifications, equivalents, improvements, and the like, which are within the spirit and principles of the one or more embodiments in the present application, are therefore intended to be included within the scope of the present disclosure.
Claims (10)
1. A method for preparing poly (3, 4-dioxyethylene thiophene) nanometer patterns by micelle etching is characterized by comprising the following steps,
1) Treating the substrate, namely treating the glass substrate by using mixed plasma gas of water and inert gas after the glass substrate is cleaned, removing and hydroxylating organic impurities on the surface of the glass substrate, and then placing the glass substrate in an environment with the humidity of 40-80% for a period of time to enable the glass substrate to absorb water until the water is balanced;
2) Spin-coating an oxide film, dripping an oxidant solution onto a glass substrate, controlling the ambient temperature to be 8-12 ℃, rotating the glass substrate to form the oxidant film on the glass substrate, and standing for a period of time after the rotation is completed; in the oxidant solution, the oxidant is ferric methylbenzenesulfonate, the solvent is n-butanol, and the oxidant solution also contains polyoxypropylene polyoxyethylene block copolymer;
3) Forming poly (3, 4-dioxyethylene thiophene) nano patterns, placing a glass substrate with an oxidant film in a gas phase synthesis chamber, heating 3, 4-dioxyethylene thiophene monomers to form 3, 4-dioxyethylene thiophene monomer steam in the gas phase synthesis chamber, controlling the humidity in the gas phase synthesis chamber to be 35-45%, controlling the temperature to be 13-17 ℃, reacting for a period of time, cleaning, and drying to obtain the poly (3, 4-dioxyethylene thiophene) nano patterns.
2. The method of claim 1, wherein in step 1), the glass substrate is cleaned by ultrasonic cleaning and then by a mixed plasma gas of water and argon.
3. The method of claim 1, wherein the iron methylbenzenesulfonate is present in the oxidant solution at a concentration of 6% by weight.
4. The method of claim 1, wherein the mass concentration of the polyoxypropylene polyoxyethylene block copolymer in the oxidizer solution is 0.1%.
5. The method of claim 1, further comprising 2 wt.% ethylene-bis-urethane diol in the oxidizer solution.
6. The method according to claim 1, wherein in step 2), the rotation control program for rotating the glass substrate is sequentially 500 rpm for 5 seconds; 2500 rpm, 30 seconds; 500 revolutions, 5 seconds.
7. The method of claim 1, wherein in step 2), the standing time after completion of the rotation is 2 minutes.
8. The process according to claim 1, wherein in step 3), the heating temperature of the 3, 4-dioxyethylenethiophene monomer is 70 ℃.
9. The method according to claim 1, wherein in step 3), the unreacted components are washed out with absolute ethanol.
10. The method according to claim 1, wherein in step 3), the sample is dried by vacuum drying at 80 ℃ in a vacuum drying oven.
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